论文标题
激发状态平均场理论的自我一致的场合
A Self Consistent Field Formulation of Excited State Mean Field Theory
论文作者
论文摘要
我们表明，与Hartree Fock理论一样，激发态平均场理论的轨道可以通过自洽的单电子方程进行优化，在该方程中，通过平均野外算子来解释电子电子排斥。除了表明这种激发的状态ANSATZ足够接近平均野外产品状态以接收单电子公式外，此方法还将轨道优化速度带到了大约两个基态均值场理论的一倍之内。该方法以多种方式与Hartree Fock理论相似，包括换向器条件的存在，单电子平均场工作方程以及通过迭代子空间中的直接反转加速。当与基于准Newton Descent的先前方法相比，与以前的方法相比，与以前的方法相比，自我一致的场合配置戴维森求解器结合使用戴维森求解器时，自我一致的场公式会大大降低理论的成本。
We show that, as in Hartree Fock theory, the orbitals for excited state mean field theory can be optimized via a self-consistent one-electron equation in which electron-electron repulsion is accounted for through mean field operators. In addition to showing that this excited state ansatz is sufficiently close to a mean field product state to admit a one-electron formulation, this approach brings the orbital optimization speed to within roughly a factor of two of ground state mean field theory. The approach parallels Hartree Fock theory in multiple ways, including the presence of a commutator condition, a one-electron mean-field working equation, and acceleration via direct inversion in the iterative subspace. When combined with a configuration interaction singles Davidson solver for the excitation coefficients, the self consistent field formulation dramatically reduces the cost of the theory compared to previous approaches based on quasi-Newton descent.
